Preparation of Gold-modified Magnetic Graphene-based Molecularly Imprinted Composites and Electrochemical Sensing Detection of Dinbutyl Phthalate in Water†

doi:10.7503/cjcu20180521

Abstract

Abstract:

Gold-modified magnetic graphene(Au@Fe₃O₄@RGO) was used as a carrier to select gold-modified magnetic properties and using surface molecular imprinting technique to select dinbutyl phthalate(DBP) as a template molecule in water environment. Graphene-based molecularly imprinted composite membrane(Au@Fe₃O₄@RGO-MIP) was prepared and characterized by means of transmission electron microscopy(TEM), X-ray diffraction(XRD) and Fourier transform infrared spectroscopy(FTIR). Au@Fe₃O₄@RGO-MIP was used as the sensitive material for sensor identification components. The performance of molecularly imprinted electrochemical sensors was analyzed by cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS) and differential pulse(DPV). The results show that the equilibrium time of the molecularly imprinted electrochemical sensor for dinbutyl phthalate in water environment is 6 min. In the concentration range of 0.01—0.1 μmol/L, there is a good linear relationship between DBP concentration and response current. The minimum detection limit is 0.3049 nmol/L(S/N=3).

Key words: Molecular imprinting technique, Graphene, Gold nanoparticle, Sensor, Phthalate

CLC Number:

O657.15

TrendMD:

LI Ying, KANG Junjun, ZHAO Xueru, XU Wenkai, QI Qi. Preparation of Gold-modified Magnetic Graphene-based Molecularly Imprinted Composites and Electrochemical Sensing Detection of Dinbutyl Phthalate in Water^†[J]. Chem. J. Chinese Universities, 2019, 40(3): 448.

Figures/Tables 12

Scheme 1 Construction and detection of electrochemical sensor modified by gold modified magnetic graphene-based molecularly imprinted composites

Fig.1 TEM images of Au@RGO(A), Fe3O4@RGO(B), Au@Fe3O4@RGO(C) and Au@Fe3O4@RGO-MIP(D)

Fig.2 XRD patterns of Au@RGO(a), Fe3O4@RGO(b) and Au@Fe3O4@RGO(c)

Fig.3 FTIR spectra(A) of GO(a), Au@RGO(b), Fe3O4@RGO(c), Au@Fe3O4@RGO(d) and Au@Fe3O4@RGO-MIP(e) and ultraviolet(UV) spectra(B) of Au@RGO(a), Au@Fe3O4@RGO(b) and Au@Fe3O4@RGO-MIP(c)

Fig.4 CV curves of Au@RGO(a), Au@Fe3O4@RGO(b), Au@Fe3O4@RGO-MIP(c), Au@Fe3O4@RGO-MIP(d) after binding templateCV curves were recorded between -0.5 V to 0.5 V in 5 mmol/L K3[Fe(CN)6] solution containing 0.1 mol/L KCl at a scan rate of 50 mV/s.

Fig.5 Electrochemical impedance spectra of Au@RGO(a), Au@Fe3O4@RGO(b)(A), Au@Fe3O4@RGO-MIP(a) and Au@Fe3O4@RGO-MIP(b)(B) after binding templateEIS of various electrodes were recorded between -0.5 V to 0.5 V in 5 mmol/L K3[Fe(CN)6] solution containing 0.1 mol/L KCl at a scan rate of 50 mV/s.

Fig.6 CV curves of DBP detectionCV curves of various electrodes were recorded between -0.5 V to 0.5 V in 0.1 mol/L PBS solution at a scan rate of 50 mV/s.

Fig.7 Adsorption kinetic curve on the response to DBP for Au@Fe3O4@RGO-MIPs electrode in PBS solution containing 10 μmol/L DBPThe insert is the DBP for Au@Fe3O4@RGO-MIP at different times. DPV of various electrodes were recorded between -0.5 V to 0.5 V in 0.1 mol/L PBS solution at a scan rate of 50 mV/s, the amplitude of 50 mV, the pulse width of 50 ms, pulse cycle of 200 ms.

Fig.8 Different concentration curves of DBP on Au@Fe3O4@RGO-MIP and Au@Fe3O4@RGO-NIP(A) and linear relationship curve of Au@Fe3O4@RGO-MIP detects DBP(B)Inset is the DPV curves of Au@Fe3O4@RGO-MIP for different concentrations of DBP. DPV of various electrodes were recorded between -0.5 V to 0.5 V in 0.1 mol/L PBS solution at a scan rate of 50 mV/s, the amplitude of 50 mV, the pulse width of 50 ms, pulse cycle of 200 ms.

Table 1 Comparison with the other electrochemical sensors for determination of DBP

Sensor	LOD/(nmol·L^-1)	Linear range/(μmol·L^-1)	Ref.
MWCNTs@GONRs/GCE	25.15	1.44—229.93	[12]
DBP-MMIP-CL	2.09	20.8—38400	[37]
MGO@Au NPs-MIPs	0.80	2.5—5	[38]
Nano-Ni(OH)₂ QCM	17.96	0.018—0.072	[39]
Au@Fe₃O₄@RGO-MIP	0.305	0.01—0.1	This work

Fig.9 Response currents of Au@Fe3O4@RGO-MIP and Au@Fe3O4@RGO-NIP for DBP, DNHP, DNOP, DINP and DIDP analogs

Fig.10 Response curve of Au@Fe3O4@RGO-MIP modified electrode to DBP concentration in lake water(A) and reproducibility of Au@Fe3O4@RGO-MIP for the detection of DBP(B)Inset of (A) is the calibration curve.

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